Table Of ContentBioenergetics and Thermodynamics: Model Systems
NATO ADVANCED STUDY INSTITUTES SERIES
Proceedings of the Advanced Study Institute Programme, which aims
at the dissemination of advanced knowledge and
the formation of contacts among scientists from different countries
The series is published by an international board of publishers in conjunction
with NATO Scientific Mfairs Division
A Life Sciences Plenum Publishing Corporation
B Physics London and New York
C Mathematical and D. Reidel Publishing Company
Physical Sciences Dordrecht, Boston and London
D Behavioural and Sijthoff & Noordhoff International
Social Sciences Publishers
E Applied Sciences Alphen aan den Rijn and Germantown
U.S.A.
Series C - Mathematical and PhYSical Sciences
Volume 55 - Bioenergetics and Thermodynamics: Model Systems
Bioenergetics
and Thennodynamics:
Model Systems
Synthetic and Natural Chelates and Macrocycles
as Models for Biological and Pharmaceutical Studies
Proceedings of the NATO Advanced Study Institute
held at Tabiano, Parma, Italy,
May 21-June 1, 1979
Edited by
A. BRAIBANTI
Faculty ofP harmacy, UniJlersity of Parma, Parma, Italy
D. Reidel Publishing Company
Dordrecht : Holland I Boston: U.S.A. I London: England
Published in cooperation with NATO Scientific Affairs Division
library of Congress Cataloging in Publication Data
NATO Advanced Study Institute, Salsomaggiore, Italy,1979.
Bioenergetics and thermodynamics.
(NATO advanced study institutes series: Series C, Mathematical and
physical sciences; v. 55).
1. Complex compounds-Congresses. 2. Chelates-Congresses.
3. Thermodynamics-Congresses. 4. Bioenergetics-Congresses.
I. Braibanti, A. II. Title. III. Series.
QPSOl.C75N37 1979 574.19'2 80-15611
ISBN -13:97S-94-009-9037 -1 e-ISBN-13:97S-94-009-9035-7
DOl: 10.1007/978-94-009-9035-7
Published by D. Reidel Publishing Company
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TABLE OF CONTENTS
PREFACE ix
A. Braibanti
BIOENERGETICS AND THERMODYNAMICS.
AIMS AND METHODOLOGY OF THE SCHOOL 1
B. Sarkar
DESIGN OF PEPTIDE MOLECULES TO MIMIC THE METAL
BINDING SITES OF PROTEINS 7
J.M. Sturtevant
CALORIMETRY AND BIOLOGY 17
B. Sarkar
BIOINORGANIC CHEMISTRY OF NICKEL 23
J.P. Sauvage
DESIGN AND SYNTHESIS OF LIGANDS 33
J.F. Stoddart
HOLES, HANDEDNESS, HANDLES, AND HOPES: MEETING THE
REQUIREMENTS OF PRIM~RY BINDING, CHIRALITY, SECONDARY
INTERACTIONS AND FUNCTIONALITY IN ENZYME ANALOGUES 43
J.P. Sauvage
TESTING OF LIGANDS 63
J.J. Christensen
CALORIMETRIC TECHNIQUES TO STUDY PROTON-LIGAND
AND METAL-LIGAND INTERACTIONS 75
P. Paoletti
STRUCTURAL AND ENERGETIC ASPECTS OF METAL-LIGAND BINDING 93
J.J. Christensen
TRANSPORT OF METAL IONS BY LIQUID MEMBRANES
CONTAINING MACROCYCLIC CARRIERS III
vi TABLE OF CONTENTS
A. Braibanti
ENTHALPY, FREE-ENERGY, AND ENTROPY DATA FOR
STRUCTURE-ACTIVITY RELATIONSHIPS IN ACIDS AND BASES 127
R.F. Jameson
POTENTIOMETRIC AND SPECTROSCOPIC DETERMINATION
OF EQUILIBRIUM CONSTANTS 145
A. Vacca
EXPERIMENTAL DATA IN CHEMICAL AND
BIOLOGICAL SYSTEMS AT EQUILIBRIUM 157
R.F. Jameson
WHAT CONCENTRATION SCALE? WHAT STANDARD
STATE? WHAT SPECIES ARE PRESENT? 165
A. Vacca
TREATMENT AND ANALYSIS OF EQUILIBRIUM
DATA BY COMPUTERS 175
G. Ostacoli
MIXED COMPLEXES 181
T. Keleti
KINETICS AND THERMODYNAMICS OF ENZYME
ACTION AND REGULATION 207
P.M. May
COMPUTER MODELS OF BIOLOGICAL SYSTEMS 221
D.E. Fenton
MEMBRANES, ALKALI METALS AND TRANSFER 229
J. Jagur-Grodzinski
SYNTHETIC SOLVENT-POLYMERIC MEMBRANES
AND THEIR TRANSPORT CHARACTERISTICS 253
D.E. Fenton
MACROCYCLES AND CATION SELECTIVITY 275
J. Jagur-Grodzinski
SELECTIVITY OF MEMBRANES TOWARDS IONS AND MOLECULES 297
G. Scibona
TRANSPORT PHENOMENA ACROSS SOLID AND LIQUID MEMBRANES 313
A. GHozzi
CARRIERS AND CHANNELS IN ARTIFICIAL
AND BIOLOGICAL MEMBRANES 339
TABLE OF CONTENTS vii
G. Scibona
LIPID BILAYER ELEeTROCHEMISTRY AND
ROLE OF THE CARRIERS 355
A. Gliozzi
THE LIPID BILAYER: A MODEL SYSTEM
FOR BIOLOGICAL MEMBRANES 377
J .M. Sturtevant
DIFFERENTIAL SCANNING CALORIMETRY.
PROCESSES INVOLVING PROTEINS 391
J .M. Sturtevant
RECENT ADVANCES IN BIOCHEMICAL CALORIMETRY 397
R. Lumry
INTERPRETATION OF CALORIMETRIC DATA
FROM COOPERATIVE SYSTEMS 405
J.P. Behr
SELECTIVE COMPLEXATION OF AMMONIUM AND GUANIDINIUM
SALTS BY SYNTHETIC RECEPTOR MOLECULES 425
R. Lumry
DYNAMICAL ASPECTS OF SMALL-MOLECULE
PROTEIN INTERACTION 435
J.M. Lehn
MOLECULAR RECEPTORS, CARRIERS AND CATALYSTS:
DESIGN, SCOPE AND PROSPECTS 455
R. Os terberg
METAL IONS IN BIOLOGICAL SYSTEMS 463
R. Osterberg
METAL ION - PROTEIN INTERACTIONS IN SOLUTIONS 465
J.M. Sturtevant
FINAL COM1ENTS 467
Contributing authors 473
PREFACE
This book reports the text of the lectures given at Tabiano, Sal so
maggiore, Italy, during the Summer School on Bioenergetios and
Thermodynamios: ModeZ Systems, in May 1979.
The aim of the School has been that of trying to employ the
thermodynamic data on synthesised organic compounds with special
reference to macrocylic ligands for the interpretation and predic
tion of energetic processes involving small and large molecules.
A detailed description of the origin, scope and plan of the
School can be found in the introductory lecture by A. Braibanti.
In appendix to this lecture there are listed some introductory
books recommended to achieve a sufficient background in the differ
ent scientific fields contributing to the School.
The audience consisted of about a hundred scientists belong
ing to different fields. Physical, organic, inorganic, pharmaceut
ical, analytical and medicinal chemists, biochemists, biophysicists,
pharmacologists interested in the problems of calorimetry, poten
tiometry, spectroscopy, transport properties of synthetic and natu
ral chelates and macromolecules spent two weeks to discuss topics
ranging from thermodynamics to electrochemistry, from measurements
on pure compounds to determinations on membranes. This picture of
the audience is an indication of researchers which can be interested
in this book.
I hope that the tremendous effort to put together scientists
working in different fields for an interdisciplinary approach to
the problem of the models for bioenergetics will be rewarded by a
good appreciation of the book and by the flowering of the scien
tific researches from the many seeds sown at the School.
A. Braibanti
ix
A.Braibtlnti (ed.), Bioenergetic, and Thermodynamic:r: Model Syatema, be.
Copyright c> 1980 by D. Reidel Publilfhing Company.
BIOENERGETICS AND THERMODYNAMICS.
AIMS AND METHODOLOGY OF THE SCHOOL
A. Braibanti
Institute of Pharmaceutical Chemistry,
University of Parma, Italy
1. INTRODUCTION
The field of bioenergetics represents a link between the energetic
phenomena in vivo and the thermodynamic interpretations of data
from many chemical compounds designed and synthesised by organic
chemists (1). Clearly, an interdisciplinary approach to the problem
is necessary in order to compare different expertises and the lan
guages of the physical, chemical, and life sciences.
The current state of knowledge in thermodynamics and in thermo
chemistry is adequate and poised for such a union. The determination
of the equilibrium constants for chemical reactions by potentiometry
and other experimental methods (2),(3),(4),(5) has recently taken
advantage of automatic measurements (6) and computerized treatment
of data (7). In thermochemistry also the possibility of automatic
monitoring equipment (8) has permitted the measurement of small
amounts of heats, even in sophisticated biological systems (9).
Simultaneously, as precise thermodynamic and thermochemical
data are collected (10), (11), (12), (13), (14), the possibility
of using them to interpret chemical and biochemical processes be
comes more realistic. However, the circulation of these data amongst
thermochemists, organic chemists, biologists, biophysicists, and
medicinal chemists is disencouraged by the difficulties of inter
preting the data because of the different presentations and the
incompleteness of our knowledge of the species present in the sys
tems concerned. A common dialogue in bioenergetics (15) can only be
achieved through an interdisciplinary discussion meeting. This is
the primary objective of the Summer School.
A. Braibanti (ed.), Bioenergetics and Thermodynamics: Model Systems, 1-6.
Copyright © 1980 by D. Reidel Publishing Company.
2 A. BRAIBANTI
2. GENERAL SCIENTIFIC. PLAN
The general plan for the School follows the usual sequence of con
siderations involved in research concerning compounds that mimic the
behaviour of naturally occurring species.
In the first instance, we try to combine our knowledge of
biochemical and biological facts and our skills in synthesising
organic ligands that may be expected to mimic the chelation and
basicity properties of in vivo processes with respect to protons
and cations (1), (16). In this context the macrocyclic ligands
represent a very good example and a very promising field of study.
Next, the problem of the choice of experimental methods for measur
ing the equilibria between ligands and metal ions is to be tackled
and, eventually, the structure of the solid complexes is determined
using crystallographic analysis (17).The thermochemical analysis
of the systems gives further insight into complexation processes,
and in particular it enphasises the role of the solvent (18), (19).
Similarly, the complexing processes involved in a mixture of
metal ions, protons, drugs, and proteins as measured from its endo-,
or exothermicity is intimately related with changes in the con
formation of the macromolecules, of the drugs, and of the solvent
(20), (21). This aspect is usually investigated by employing anal
ogous arguments based upon previous experience with the thermodyn
amic investigations of simpler systems; these are essential in
order to understand the selectivity of ligands towards metal ions
and anions. This subject is considered also in connection with
properties of membrane carriers and antibiotics (22), (23).
Both thermodynamic and kinetic aspects of the problem have
to be discussed in order to get a realistic picture of the bio
logical processes occurring (24).
This information, concepts, and data are the fundamental basis
to discuss the important applications of calorimetry to biological
systems (25) and the bioenergetics of drug-receptor interactions
(26).
3. BACKGROUND INFORMATION AND FRONTIER TOPICS
The topics to be discussed at the Summer School are drawn from
diverse disciplines and we shall assume that each participant
possesses a good knowledge, not only of his or her own field, but
also a reading knowledge of the other fields concerned. Such an
acquaintance with the subject can be obtained by studying the in
troductory books, of the list which had been compiled when the
project of the School started. The list (s. Appendix) is by no
means exhaustive but would serve as a guide for teachers when
discussing with the students.
